Aromatic-Aromatic Interactions Induce the Self-Assembly of Pentapeptidic Derivatives in Water To Form Nanofibers and Supramolecular Hydrogels
Aromatic-Aromatic Interactions Induce the Self-Assembly of Pentapeptidic Derivatives in Water To Form Nanofibers and Supramolecular Hydrogels
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DOI：
10.1021/ja9088764
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发表时间：
2010-03-03
影响因子：
15
通讯作者：
Xu, Bing
中科院分区：
文献类型：
--
作者：
Ma, Manlung;Kuang, Yi;Xu, Bing
在本文中，我们报道了芳香族部分(P、F或N)与五肽GAGAS(1)、GVPVP(2)、VPGVG(3)、VTEEI(4)、VYGGG(5)和YGFGG(6)的偶联反应，为探索基于五肽的水凝胶提供了潜在的生物材料。大多数这些化合物(1F、1P、2F、2P、4F、4P、4N、5F、5N、6F、6P和6N)表现为分子水凝胶，在凝胶的最低浓度为0.5-2.8wt%时可以形成水凝胶。水凝胶的荧光光谱显示出明显的红移，表明这些水凝胶中的芳香族部分之间存在相互作用。圆二色谱表明，水凝胶剂的自组装提供了螺旋状或β片状结构。透射和扫描电子显微镜检查揭示了这些水凝胶剂的纳米纤维网络。此外，流变学测量表明，这些水凝胶的粘弹性性能一般至极好。这些水凝胶分子间芳香相互作用和氢键的平衡；导致它们在水中自组装并形成纳米纤维作为水凝胶的基质。在测试的条件下，这18个五肽衍生物中共有6个-1N、2N、3F、3P、3N和5P-不能形成水凝胶，这可能是由于分子间相互作用不平衡所致。这项工作表明，芳香族相互作用是形成分子纳米纤维和超分子水凝胶的有用和有利的作用力。
In this paper we report the conjugation of an aromatic moiety (pyrene (P), fluorene (F), or naphthalene (N)) to pentapeptides GAGAS (1), GVPVP (2), VPGVG (3), VTEEI (4), VYGGG (5), and YGFGG (6) to afford peptidic derivatives for exploring pentapeptide-based hydrogels as potential biomaterials. Most of these compounds (1F, 1P, 2F, 2P, 4F, 4P, 4N, 5F, 5N, 6F, 6P, and 6N) behave as molecular hydrogelators and can form hydrogels at minimum concentrations of gelation from 0.5 to 2.8 wt%. The fluorescence spectra of the hydrogels exhibit a significant red shift, indicating the interactions between the aromatic moieties in those hydrogels. The circular dichroism spectra indicate that the self-assembly of the hydrogelators; affords helical or beta-sheet-like structures. Transmission and scanning electron microscopic examination reveals the nanofiber networks of these hydrogelators. In addition, rheological measurements show fair to excellent viscoelastic properties of these hydrogels. The balance of intermolecular aromatic-aromatic interactions and hydrogen bonds of these hydrogelators; leads to their self-assembly in water and the formation of nanofibers as the matrixes of hydrogels. A total of 6 of these 18 pentapeptide derivatives-1N, 2N, 3F, 3P, 3N, and 5P-fail to form hydrogels under the conditions tested, likely due to unbalanced intermolecular interactions. This work suggests that aromatic-aromatic interactions are useful and favorable forces for creating molecular nanofibers and supramolecular hydrogels.